CN1537919A - Liquid crystal polyester solution composition - Google Patents
Liquid crystal polyester solution composition Download PDFInfo
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- CN1537919A CN1537919A CNA2004100316960A CN200410031696A CN1537919A CN 1537919 A CN1537919 A CN 1537919A CN A2004100316960 A CNA2004100316960 A CN A2004100316960A CN 200410031696 A CN200410031696 A CN 200410031696A CN 1537919 A CN1537919 A CN 1537919A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60N—SEATS SPECIALLY ADAPTED FOR VEHICLES; VEHICLE PASSENGER ACCOMMODATION NOT OTHERWISE PROVIDED FOR
- B60N2/00—Seats specially adapted for vehicles; Arrangement or mounting of seats in vehicles
- B60N2/24—Seats specially adapted for vehicles; Arrangement or mounting of seats in vehicles for particular purposes or particular vehicles
- B60N2/26—Seats specially adapted for vehicles; Arrangement or mounting of seats in vehicles for particular purposes or particular vehicles for children
- B60N2/28—Seats readily mountable on, and dismountable from, existing seats or other parts of the vehicle
- B60N2/2866—Seats readily mountable on, and dismountable from, existing seats or other parts of the vehicle booster cushions, e.g. to lift a child to allow proper use of the conventional safety belts
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/60—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from the reaction of a mixture of hydroxy carboxylic acids, polycarboxylic acids and polyhydroxy compounds
- C08G63/605—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from the reaction of a mixture of hydroxy carboxylic acids, polycarboxylic acids and polyhydroxy compounds the hydroxy and carboxylic groups being bound to aromatic rings
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60N—SEATS SPECIALLY ADAPTED FOR VEHICLES; VEHICLE PASSENGER ACCOMMODATION NOT OTHERWISE PROVIDED FOR
- B60N2/00—Seats specially adapted for vehicles; Arrangement or mounting of seats in vehicles
- B60N2/24—Seats specially adapted for vehicles; Arrangement or mounting of seats in vehicles for particular purposes or particular vehicles
- B60N2/26—Seats specially adapted for vehicles; Arrangement or mounting of seats in vehicles for particular purposes or particular vehicles for children
- B60N2/265—Adaptations for seat belts
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/685—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen
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- General Health & Medical Sciences (AREA)
- Aviation & Aerospace Engineering (AREA)
- Child & Adolescent Psychology (AREA)
- Mechanical Engineering (AREA)
- Polyamides (AREA)
- Polyesters Or Polycarbonates (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Liquid Crystal Substances (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
Provided are a liquid crystal type polyester solution composition which is improved in corrosion resistance, shows an optical anisotropy when molten at a temperature below 450 deg.C and is easily treated, a method for preparing a liquid crystal type polyester film by using the composition and a liquid crystal type polyester film prepared by the method which has a low anisotropic mechanical strength. The liquid crystal type polyester solution composition comprises 100 parts by weight of an aprotic solvent; and 0.01-100 parts by weight of a liquid crystal type polyester which comprises 10-35 mol% of at least one repeating unit selected from the group consisting of a repeating unit derived from an aromatic diamine, a repeating unit derived from an aromatic amine having a hydroxyl group and a repeating unit derived from an aromatic amino acid.
Description
Technical field
The invention relates to a kind of liquid crystal polyester (liquid-crystalline polyester) solution composition thing.
Background technology
Liquid crystal polyester has excellent dielectric properties and low water absorbable in high frequency, therefore often be used as the material of electronic substrate.If utilize the mode of extruding liquid crystal polyester to produce film, the molecular chain of this polyester can be along the direction of extruding.Because this directivity is, the physical strength of film is iso in horizontal direction (the vertical direction of extrusion) right and wrong, and it is compared to longitudinal direction (direction of extrusion).
Generation method with liquid crystal polyester thin film of little anisotropic, can contain liquid crystal polyester and trifluoroacetic solution on a upholder by coating one, the mode that removes solvent is again made afterwards, it is to be exposed among the JP 62-64832A, yet the employed solvent of JP 6264832A has highly corrosive, therefore is difficult to handle or operation.
The disclosed liquid crystal polyester liquid of JP 2002-114894A is to comprise solvent, and it for example is a p-chlorovinyl ketone, with as the low-corrosiveness solvent.And the present invention proposes another kind of solution composition thing, and it has lower corrodibility thereby is easier to handles, and a kind of liquid crystal polyester thin film with little anisotropic physical strength is provided.
Summary of the invention
The objective of the invention is to, in order to overcome the defective that existing liquid crystal polyester liquid exists, and provide a kind of liquid crystal polyester liquid constituent, technical problem to be solved is to make it have lower corrodibility, thereby is easier to handle, thereby is suitable for practicality more.
Another object of the present invention is to, a kind of liquid crystal polyester thin film is provided, technical problem to be solved is to make a kind of liquid crystal polyester thin film with little anisotropic physical strength is provided.
The object of the invention to solve the technical problems realizes by the following technical solutions.A kind of liquid crystal polyester liquid constituent according to the present invention's proposition, it comprises a non-protonic solvent and a liquid crystal polyester, this liquid crystal polyester comprises a repeating unit at least, its be selected from by fragrant diamine derive and the repeating unit that comes, by the aromatic amine with hydroxyl derive and the repeating unit that comes and by aromatic amino acid derive and cohort that the repeating unit that comes is formed one of them, and this repeating unit accounts for 10～35% molar percentages at this liquid crystal polyester.
The object of the invention to solve the technical problems also can be applied to the following technical measures to achieve further.
Aforesaid liquid crystal polyester liquid constituent, this included repeating unit of wherein said liquid crystal polyester is to be expressed as chemical formula (1), (2), (3), and chemical formula (1), (2), (3) repeating unit are to account for 30～80% molar percentages, 10～35% molar percentages, 10～35% molar percentages respectively at this liquid crystal polyester: (1)-O-Ar
1-CO-; (2)-CO-Ar
2-CO-; (3)-X-Ar
3-Y; Ar wherein
1Expression 1,4-phenylbenzene, 2,6-naphthyl or 4,4 '-two phenylbenzene, Ar
2Expression 1,4-phenylbenzene, 1,3-phenylbenzene or 2,6-naphthyl, Ar
3Expression 1,4-phenylbenzene or 1,3-phenylbenzene, X represent-NH-, and Y represents-O-or-NH-.
Aforesaid liquid crystal polyester liquid constituent, the amount of wherein said liquid crystal polyester are between 0.01 to 100 part of weight, and it is for this non-protonic solvent of 100 parts of weight.
Aforesaid liquid crystal polyester liquid constituent, wherein said non-protonic solvent are for not having the non-protonic solvent of halogen atom.
Aforesaid liquid crystal polyester liquid constituent, wherein said non-protonic solvent are to be 3～5 non-protonic solvent for having moment of dipole.
Aforesaid liquid crystal polyester liquid constituent, wherein said to have moment of dipole be that 3～5 non-protonic solvent is to be ester solvent in an acid amide solvent or.
Aforesaid liquid crystal polyester liquid constituent, wherein said acid amide solvent is to be selected from N, N '-dimethyl formamide, N, N '-N,N-DIMETHYLACETAMIDE and N-methyl cough up cohort that pyridine ketone formed one of them.
Aforesaid liquid crystal polyester liquid constituent, wherein said Ar
1Be to be 2,6-naphthyl, Ar
2Be to be 1,3-phenylbenzene, Ar
3Be to be 1,4-phenylbenzene, X are to be-NH-, and Y is-O-.
The object of the invention to solve the technical problems also adopts following technical scheme to realize.According to a kind of method of producing liquid crystal polyester thin film that the present invention proposes, it may further comprise the steps: this above-mentioned solution composition thing is coated on the upholder; And remove this solvent.
The object of the invention to solve the technical problems also adopts following technical scheme to realize.According to a kind of liquid crystal polyester thin film that the present invention proposes, it is the method production by above-mentioned production liquid crystal polyester thin film.
The present invention compared with prior art has tangible advantage and beneficial effect.By above technical scheme as can be known, in order to reach aforementioned goal of the invention, the present inventor drops into suitable painstaking effort research to find out a kind of liquid crystal polyester liquid constituent, and it has low-corrosiveness and easy-to-handle advantage.This solution composition thing comprises a non-protonic solvent and a liquid crystal polyester, and this liquid crystal polyester comprises by aromatic amine derivant derives and next repeating unit.This solution composition thing can provide the liquid crystal polyester thin film with little anisotropic physical strength.
Liquid crystal polyester liquid constituent of the present invention, it comprises a non-protonic solvent and a liquid crystal polyester, this liquid crystal polyester comprises a repeating unit at least, its be selected from by fragrant diamine derive and the repeating unit that comes, by the aromatic amine with hydroxyl derive and the repeating unit that comes and by aromatic amino acid derive and cohort that the repeating unit that comes is formed one of them, and repeating unit accounts for 10～35% molar percentages at liquid crystal polyester.
In sum, the liquid crystal polyester liquid constituent of special construction of the present invention, have above-mentioned many advantages and practical value, and in like product, do not see have similar structure design and method to publish or use and really genus innovation, though its structurally, on the method or bigger improvement all arranged on the function, have technically than much progress, and produced handy and practical effect, and more existing liquid crystal polyester liquid has the multinomial effect of enhancement, thereby be suitable for practicality more, and have the extensive utility value of industry, really be a new and innovative, progressive, practical new design.
Above-mentioned explanation only is the general introduction of technical solution of the present invention, for can clearer understanding technique means of the present invention, and can be implemented according to the content of specification sheets, below with preferred embodiment of the present invention and conjunction with figs. describe in detail as after.
Embodiment
Reach technique means and the effect that predetermined goal of the invention is taked for further setting forth the present invention, below in conjunction with preferred embodiment, to its embodiment of liquid crystal polyester liquid constituent, structure, feature and the effect thereof that foundation the present invention proposes, describe in detail as after.
Be used for liquid crystal polyester of the present invention and comprise a repeating unit, it is to be selected from by fragrant diamine to derive and the repeating unit that comes, derived and the repeating unit that comes or derived and the repeating unit that comes by aromatic amino acid by the aromatic amine with hydroxyl, or two or more above-mentioned repeating units.
The content of above-mentioned repeating unit accounts for 10～35% molar percentages of liquid crystal polyester.If when liquid crystal polyester comprised two or more repeating units, its total content was between 10～35% molar percentages.
Being used for aromatic liquid crystal polyester of the present invention, is to be a kind of polyester, and it is called tropism's liquid crystal polyesters such as heat, and it can demonstrate the optics anisotropic when 450 degree Celsius or lower melt temperature.
The included repeating unit of preferable liquid crystal polyester is to be expressed as chemical formula (1), (2), (3), and is as follows.And chemical formula (1), (2), (3) repeating unit preferably account for 30～80% molar percentages, 10～35% molar percentages, 10～35% molar percentages respectively in liquid crystal polyester:
(1)-O-Ar
1-CO-
(2)-CO-Ar
2-CO-
(3)-X-Ar
3-Y
In above-mentioned chemical formula, Ar
1Expression 1,4-phenylbenzene, 2,6-naphthyl or 4,4 '-two phenylbenzene, Ar
2Expression 1,4-phenylbenzene, 1,3-phenylbenzene or 2,6-naphthyl, Ar
3Expression 1,4-phenylbenzene or 1,3-phenylbenzene, X represent-NH-, and Y represents-O-or-NH-.
Repeating unit (1) is to be derived and next repeating unit by aromatic hydroxycarboxylic acid, repeating unit (2) is to be derived and next repeating unit by aromatic dicarboxilic acid, and repeating unit (3) is to be derived and the repeating unit that comes by fragrant diamine, and wherein fragrant diamine has hydroxyl or aromatic amino acid.Replace aromatic hydroxycarboxylic acid, aromatic dicarboxilic acid, have the hydroxyl or the fragrant diamine of aromatic amino acid, the liquid crystal polyester that comprises above-mentioned repeating unit can utilize its ester class form derivative to generate, and wherein ester class form derivative for example is the derivative with ester class form character.
Ester class form derivative with compound of carboxylic acid group comprises, for example be, have a carboxyl in one a sour muriate or the anhydride form, carry out to impel ester class to form reaction with hyperergy, or make carboxyl and alcohols, ethylene glycol and analogue form an ester class, so promptly can form a polyester by a transesterification reaction.
Ester class form derivative with compound of aromatic hydroxy group comprises, for example is, its aromatic hydroxy group can form an ester class with carboxylic acid, to form a polyester by a transesterification reaction.
Ester class form derivative with compound of amido comprises, for example is, its amido can form an ester class with carboxylic acid, to form a polyester by a transesterification reaction.
The example of the repeating unit of liquid crystal polyester used in the present invention comprises following repeating unit.
The example of repeating unit (1) comprises the repeating unit next by p-hydroxy-benzoic acid, 2-hydroxyl-6-formic acid and 4-hydroxyl-4 '-phenylbenzene carboxylic acid derivatives.Can also comprise two or more repeating units in the liquid crystal polyester.In above-mentioned repeating unit, preferable repeating unit is to be derived and next repeating unit by 2-hydroxyl-6-formic acid.
The content of repeating unit (1) preferably occupies 30～80% molar percentages in the repeating unit of total liquid crystal polyester, more preferably 40～70% molar percentages, more preferably 45～65% molar percentages.If the content of repeating unit (1) surpasses 80% molar percentage, the follow-up solubleness that is dissolved in the solvent can reduce.If the content of repeating unit (1) is lower than 30% molar percentage, liquid crystallinity will can not exist.
The example of repeating unit (2) comprises that by phthalic acid, m-phthalic acid, 2 the 6-dicarboxylic acid is derived and next repeating unit.Can also comprise two or more repeating units in the liquid crystal polyester.In above-mentioned repeating unit, preferable repeating unit is to be derived and next repeating unit by m-phthalic acid, and it is to be dissolved in the viewpoint of the solubleness in the solvent.
The content of repeating unit (2) preferably occupies 10～35% molar percentages in the repeating unit of total liquid crystal polyester, more preferably 30～15% molar percentages, more preferably 27.5～17.5% molar percentages.If the content of repeating unit (2) surpasses 35% molar percentage, liquid crystallinity will reduce.If the content of repeating unit (2) is lower than 10% molar percentage, the follow-up solubleness that is dissolved in the solvent can reduce.
The example of repeating unit (3) comprises that by 3-amine phenol, 4-amine phenol, 1 4-phenylenediamine and 1,3-phenylenediamine are derived and next repeating unit.Can also comprise two or more repeating units in the liquid crystal polyester.In above-mentioned repeating unit, preferable repeating unit is to be derived and next repeating unit by 4-amine phenol, and it is with its reactive viewpoint.
The content of repeating unit (3) preferably occupies 10～35% molar percentages in the repeating unit of total liquid crystal polyester, more preferably 30～15% molar percentages, more preferably 27.5～17.5% molar percentages.If the content of repeating unit (3) surpasses 35% molar percentage, liquid crystallinity will reduce.If the content of repeating unit (3) is lower than 10% molar percentage, the follow-up solubleness that is dissolved in the solvent can reduce.
The content of repeating unit (3) preferably equals the content of repeating unit (2) in fact.In addition, the viewpoint of the extent of polymerization of the liquid crystal polyester of obtaining from control, the content of repeating unit (3) preferably between the content of repeating unit (2) ± 10% molar percentage between.
The method of producing aromatic liquid crystal polyester of the present invention is not limited especially; it can be the hydroxyl in aromatic hydroxycarboxylic acid or amido provides repeating unit (1) for example; the fragrance diamine, has hydroxyl or the aromatic amine of aromatic amino acid provides repeating unit (3); its be with an excess fats acid anhydrides acidylate obtaining an acylated compounds, and acylated compounds and provide the transesterification between the aromatic dicarboxilic acid of repeating unit (2) promptly can form liquid crystal polyester.Identical with acylated compounds, the fatty acid ester of obtaining by previous acidylate can also use.(JP Nos.2002-22044A and 2002-146003A)
The content of the fatty acid anhydride in acylation reaction, preferably phenolic hydroxyl group is normal 1.05～1.2 times, and preferably phenolic hydroxyl group is normal 1.05～1.1 times.If the content of the fatty acid anhydride that adds is lower than normal 1.0 times of phenolic hydroxyl group, in transesterification reaction (polycondensation reaction) process, acylated compounds, aromatic hydroxycarboxylic acid and aromatic dicarboxilic acid may distil, and the pipeline of reaction vessel may block.If the content of the fatty acid anhydride that adds is higher than normal 1.2 times of phenolic hydroxyl group, the dyeing situation of at last obtained liquid crystal polyester may be more obvious.
Acylation reaction was preferably carried out 5 minutes to 10 hours at 130 to 180 degree Celsius, preferably carried out 10 minutes to 3 hours at 140 to 160 degree Celsius.
The fatty acid anhydride that is used for acylation reaction of the present invention is not limited especially; it can comprise; for example; acetic anhydride, propionic anhydride, butyryl oxide, isobutyric anhydride, valeric anhydride, trimethylacetic acid acid anhydride, 2 ethyl hexanoic acid, monochloro acetic anhydride, dichloroacetic acid acid anhydride, Tricholroacetic Acid acid anhydride, single bromine acetic anhydride, dibromo acetic anhydride, tri bromo acetic acid acid anhydride, single fluorine acetic anhydride, difluoro acetic anhydride, trifluoro-acetic anhydride, Pyroglutaric acid, MALEIC ANHYDRIDE, succinyl oxide, bromo-propionic acid acid anhydride and analogue, and it can two kinds or above mixing use.And from its price and easy-to-handle viewpoint, preferably acetic anhydride, propionic anhydride, butyryl oxide, isobutyric anhydride, more preferably acetic anhydride.
In transesterification reaction, the amount of the acyl group in the acylated compounds preferably is 0.8～1.2 times of carboxyl equivalent.
The carrying out of transesterification reaction preferably with Celsius 0.1～50 the degree/minute speed from Celsius 130 the degree be warming up to Celsius 400 the degree, preferably with Celsius 0.3～5 the degree/minute speed from Celsius 150 the degree be warming up to Celsius 350 the degree.
In the transesterification reaction of carboxylic acid and the fatty acid ester obtained by acylation reaction; preferably the lipid acid that is generated is a by product; and unreacted fatty acid anhydride can be distilled, and it utilizes method commonly used to carry out, and for example is that distillation method shifts the equilibrated purpose to reach.
In acylation reaction and transesterification reaction, can also add a catalyzer.And the catalyzer that is added can be the known catalyzer that is used for the polyreaction of polyester, it for example is to comprise metal salt catalyst, for example be magnesium acetate, tin acetate, tetrabutyl titanate salt, plumbic acetate, Potassium ethanoate, ANTIMONY TRIOXIDE SB 203 99.8 PCT and analogue, organic catalyst for example is N, N '-dimethyl amido pyridine, N-Methylimidazole and analogue.
In above-mentioned catalyzer, preferably contain the heterogeneous ring compound of two or more nitrogen-atoms, it for example is N, the pyridine of N ' dimethyl amido, N-Methylimidazole (JP No.2002-146003).
These catalyzer generally are to insert when inserting monomer, and do not need to remove after acylation, and if catalyzer does not remove, it can be used for transesterification reaction.
The polycondensation reaction that produces by transesterification is normally carried out in merging (melt) polyreaction, and merges polyreaction and solid-phase polymerization can use together.Preferably, in solid-phase polymerization, can merge from one and take out a polymkeric substance the polymerization processing procedure, be ground into powder type or sheet form afterwards, and use it for the method for a known solid-phase polymerization.The method of solid-phase polymerization for example is to be included in to carry out a thermal treatment in solid-state, and it is in 20～350 degree Celsius approximately and carried out 1 to 30 hour in inert atmosphere (for example being nitrogen).Solid-phase polymerization can carry out in agitation condition, also can be static and carry out in the situation that do not have to stir.In addition, merging polyreaction and solid-phase polymerization can carry out in the same reaction vessel that an agitation as appropriate mechanism can be provided.After solid-phase polymerization, can utilize known method that prepared aromatic liquid crystal polyester is made particulate state or molded in addition.
Producing the method for aromatic liquid crystal polyester, for example is to utilize batch equipment, continuous equipment or similar devices.
Traditional weighting material, additive or analogue can add in the liquid crystal polyester.
The example of weighting material comprises: organic weighting material for example is epoxy powder, melamine resin powder, carbamide resin powder, two amido phenyl, three nitrogen land surround toner and styrene resin powder; And inorganic filler, for example be silicon, aluminum oxide, titanium oxide, zirconium white, hydrated aluminium silicate, lime carbonate, calcium phosphate.
The example of additive comprises known binding reagents, shallow lake, anti-Shen reagent, UV absorption agent and thermo-stabilizer.
One or more thermoplastic resin can also add in the liquid crystal polyester.Thermoplastic resin comprise polypropylene, polymeric amide, poly-sulfuration benzene, polyetherketone, poly-carbonic acid, polyethers, polyphenylene oxide with and modified polymer and polyetherimide, elastomerics, for example be the multipolymer of methacrylic acid glycide ester and ethene, and analogue.
The solvent that is used for liquid crystal polyester liquid constituent of the present invention is to be a non-protonic solvent.The usage quantity of non-protonic solvent is not limited, and gets final product so long as can dissolve liquid crystal polyester, and may select suitable consumption according to the reality use.The amount of preferable liquid crystal polyester is 0.01 to 100 part of weight, and it is for the non-protonic solvent of 100 parts of weight.If the amount of liquid crystal polyester is lower than 0.01 part of weight, the viscosity of solution composition thing can be too low so that can not be coated with fear uniformly.If surpass 100 parts of weight, viscosity again can be too high.Based on usability and consideration economically, the amount of liquid crystal polyester preferably is not less than 1 part of weight, more preferably be not less than 2 parts of weight and be not higher than 50 parts of weight, more preferably be not higher than 40 parts of weight, it is for the non-protonic solvent of 100 parts of weight.
The example of non-protonic solvent comprises: the halogen solvent, and it for example is 1-chlorobutane, chlorobenzene, 1,1-ethylene dichloride, chloroform, sym.-tetrachloroethane; Ether solvent for example is Anaesthetie Ether, tetrahydrofuran (THF) and 1,4-dioxy land surround; Ketones solvent for example is an acetone and go back hexanone; Esters solvent for example is a vinyl acetic monomer; Interior ester solvent for example is γ-n-butyl acrylate; The carbonic ether solvent for example is vinyl carbonic ether and propenyl carbonic ether; Amine solvent for example is triethylamine and pyridine; Nitrile solvents for example is acetonitrile, acid amide solvent, for example is N, N '-dimethyl formamide, N, N '-N,N-DIMETHYLACETAMIDE, tetrahydrofuran (THF) and N-methylpyrrole pyridine ketone; The nitro solvent for example is Nitromethane 99Min. and oil of mirbane; The sulfide solvent for example is dimethyl sulfoxide (DMSO) and fourth dioxane sulfone; And the phosphide solvent, for example be hempa acid amide and three-just-butyl phosphide.
In above-mentioned solvent, preferably not halogen-containing solvent, it is with the environmental protection viewpoint.And with the viewpoint of solubleness, this preferred solvents be to have 3～5 moment of dipole.Preferably, the solvent with 3～5 moment of dipole comprises the acid amide solvent, and it for example is N, and N '-dimethyl formamide, N, N '-N,N-DIMETHYLACETAMIDE, tetrahydrochysene mutter and N-methylpyrrole pyridine ketone; And interior ester solvent, for example be γ-n-butyl acrylate.More preferably, N, N '-dimethyl formamide, N, N '-N,N-DIMETHYLACETAMIDE and N-methylpyrrole pyridine ketone.
Liquid crystal polyester thin film can utilize following manner to make.At first liquid crystal polyester is held in a non-protonic solvent to obtain a solution composition thing.If necessary, can utilize a strainer to filter this solution composition thing earlier, to remove tiny heterogeneous material in the solution composition thing.Afterwards this solution composition thing is coated on the upholder so that it is smooth and evenly, it for example is to utilize any coating process, for example is the roller coating, soaks coating, spray coating, rotary coating, heavy curtain coating, groove coating and screen coating.After coating, with solvent removal.
The method that removes non-protonic solvent is not limited especially, preferably utilizes method of evaporation.And the mode of evaporating solvent can be utilized similarly mode such as heating, decompression, ventilation.In above-mentioned method, preferably utilize the heating evaporation mode, it is the viewpoint with productive rate and easy handling.More preferably under the airy condition, heat to evaporate it.The method that heats under the airy condition comprises at first carried out drying about 10 minutes to 2 hours at 60～200 degree Celsius, heat-treated about 30 minutes to 5 hours at 200～400 degree Celsius more afterwards.
Thickness with the above-mentioned prepared liquid crystal polyester thin film of method is not limited, and preferably 0.5～500 micron, it is with the formation of film and the viewpoint of mechanical properties.Preferable be～100 microns, it is with easy-to-handle viewpoint.
The advantage that liquid crystal polyester liquid constituent of the present invention has low-corrosiveness and removes processing.And, utilize the mechanical properties of the prepared film of this solution composition thing between longitudinal direction (coating direction) and horizontal direction (perpendicular to the coating direction), to have little anisotropic, thereby have excellent physical strength.And, have excellent usefulness in high frequency, and the tool low water absorbable of liquid crystal polyester own.Therefore, this film is suitable for the film as electronic component, and it for example is a printed circuit board (PCB).
It should be noted that to comprise multiplely from being thinned to the object of thick sheet pattern at this employed " film ", and is not that only to limit be the sheet object, and it can also be the object form of other vessel form, for example is bottom thing and analogue.
Example
At this, will describe the present invention in detail, but the present invention is defined in the following example.
Production instance 1
In a reactor that is equipped with an agitator, a torquer, a nitrogen supply bobbin, a thermometer and a backflow compressor, drop into the 2-hydroxyl-6-naphthoic acid of 941 grams (5.0 moles), the 4-amine phenol of 273 grams (2.5 moles), the m-phthalic acid of 415.3 grams (2.5 moles) and the acetic anhydride of 1123 grams (11 moles).Make the interior air of reactor fully by after the nitrogen replacement, under the condition that nitrogen flows into, temperature was warming up to 150 degree Celsius above 15 minutes.Afterwards with temperature maintenance 3 hours so that its backflow.
Afterwards temperature is warming up to 320 degree Celsius and surpasses 170 minutes, to remove the by product that distills acetic acid and unreacted acetic anhydride.When torquer changes, promptly can termination reaction, and product taken out.And the content of 4-amine phenol be constitute liquid crystal polyester always repeat unitary 12% molar percentage.When using polarizing microscope to watch obtained resin, can find that it has mesomorphic phase distinctive schlieren pattern when Celsius 200 spend.
Production instance 2
In a reactor that is equipped with an agitator, a torquer, a nitrogen supply bobbin, a thermometer and a backflow compressor, drop into the p-hydroxybenzoic acid of 690 grams (5.0 moles), the 4-amine phenol of 273 grams (2.5 moles), the m-phthalic acid of 415.3 grams (2.5 moles) and the acetic anhydride of 1123 grams (11 moles).Make the interior air of reactor fully by after the nitrogen replacement, under the condition that nitrogen flows into, temperature was warming up to 150 degree Celsius above 15 minutes.Afterwards with temperature maintenance 3 hours so that its backflow.
Afterwards temperature is warming up to 320 degree Celsius and surpasses 170 minutes, to remove the by product that distills acetic acid and unreacted acetic anhydride.When torquer raises, promptly can termination reaction, and product taken out.When using polarizing microscope to watch obtained resin, can find that it has mesomorphic phase distinctive schlieren pattern when Celsius 200 spend.
Production instance 3
In a reactor that is equipped with an agitator, a torquer, a nitrogen supply bobbin, a thermometer and a backflow compressor, 4 of the 2-hydroxyl-6-naphthoic acids of input 191.8 grams (1.02 moles), 63.3 grams (0.34 mole), the m-phthalic acid of 4 '-dihydroxyl hexichol, 56.5 grams (0.34 mole) and the acetic anhydride of 191 grams (1.87 moles).Make the interior air of reactor fully by after the nitrogen replacement, under the condition that nitrogen flows into, temperature was warming up to 150 degree Celsius above 15 minutes.Afterwards with temperature maintenance 3 hours so that its backflow.
Afterwards temperature is warming up to 320 degree Celsius and surpasses 170 minutes, to remove the by product that distills acetic acid and unreacted acetic anhydride.When torquer raises, promptly can termination reaction, and product taken out.When using polarizing microscope to watch obtained resin, can find that it has mesomorphic phase distinctive schlieren pattern when Celsius 250 spend.
Production instance 4
In a reactor that is equipped with an agitator, a torquer, a nitrogen supply bobbin, a thermometer and a backflow compressor, 4 of the p-hydroxybenzoic acids of input 140.8 grams (1.02 moles), 63.3 grams (0.34 mole), the m-phthalic acid of 4 '-dihydroxyl hexichol, 56.5 grams (0.34 mole) and the acetic anhydride of 191 grams (1.87 moles).Make the interior air of reactor fully by after the nitrogen replacement, under the condition that nitrogen flows into, temperature was warming up to 150 degree Celsius above 15 minutes.Afterwards with temperature maintenance 3 hours so that its backflow.
Afterwards temperature is warming up to 320 degree Celsius and surpasses 170 minutes, to remove the by product that distills acetic acid and unreacted acetic anhydride.When torquer raises, promptly can termination reaction, and product taken out.Afterwards the solid state component of obtaining is cooled off at room temperature, utilize a coarse pressure to grind device and press and grind, and it was stayed in the nitrogen gas atmospheres of 250 degree Celsius 10 hours, so that it carries out polyreaction in solid-state.When using polarizing microscope to watch at last obtained resin, can find that it has mesomorphic phase distinctive schlieren pattern when Celsius 200 spend.
Example 1
0.5 gram is added 9.5 gram N-methylpyrrole pyridine ketone with production instance 1 prepared aromatic liquid crystal polyester, and heat is to 120 degree Celsius.Afterwards, confirm that powder has dissolved fully to form a clear solution.Stirring is with solution and remove bubble to obtain an aromatic liquid crystal polyester solution.Afterwards, utilize excellent coating method with this solution coat on Copper Foil, and heat-treat, its be 100 heating 1 hour again 250 degree heating Celsius 1 hour, can obtain the film that is pasted with Copper Foil afterwards.
Example 2
0.5 gram is added 9.5 gram N-methylpyrrole pyridine ketone with production instance 2 prepared aromatic liquid crystal polyesters, and heat is to 120 degree Celsius.Afterwards, confirm that powder has dissolved fully to form a clear solution.Stirring is with solution and remove bubble to obtain an aromatic liquid crystal polyester solution.Afterwards, utilize excellent coating method with this solution coat on Copper Foil, and heat-treat, its be 100 heating 1 hour again 250 degree heating Celsius 1 hour, can obtain the film that is pasted with Copper Foil afterwards.
Comparative example 1
0.5 gram is added 9.5 gram N-methylpyrrole pyridine ketone with production instance 3 prepared aromatic liquid crystal polyesters, and heat is to 120 degree Celsius.Found that powder can't dissolve fully.
Comparative example 2
0.5 gram is added 9.5 gram N-methylpyrrole pyridine ketone with production instance 4 prepared aromatic liquid crystal polyesters, and heat is to 120 degree Celsius.Found that powder can't dissolve fully.
According to the present invention, it can provide a kind of liquid crystal polyester liquid constituent, the advantage that it has low-corrosiveness and removes processing.And a liquid crystal polyester thin film can be provided, it has the physical strength of low anisotropic.
The above, it only is preferred embodiment of the present invention, be not that the present invention is done any pro forma restriction, though the present invention discloses as above with preferred embodiment, yet be not in order to limit the present invention, any those skilled in the art, in not breaking away from the technical solution of the present invention scope, when the technology contents that can utilize above-mentioned announcement is made a little change or is modified to the equivalent embodiment of equivalent variations, in every case be the content that does not break away from technical solution of the present invention, according to technical spirit of the present invention to any simple modification that above embodiment did, equivalent variations and modification all still belong in the scope of technical solution of the present invention.
Claims (10)
1, a kind of liquid crystal polyester liquid constituent, it is characterized in that it comprises a non-protonic solvent and a liquid crystal polyester, this liquid crystal polyester comprises a repeating unit at least, its be selected from by fragrant diamine derive and the repeating unit that comes, by the aromatic amine with hydroxyl derive and the repeating unit that comes and by aromatic amino acid derive and cohort that the repeating unit that comes is formed one of them, and this repeating unit accounts for 10～35% molar percentages at this liquid crystal polyester.
2, liquid crystal polyester liquid constituent according to claim 1, it is characterized in that this included repeating unit of wherein said liquid crystal polyester is to be expressed as chemical formula (1), (2), (3), and chemical formula (1), (2), (3) repeating unit are to account for 30～80% molar percentages, 10～35% molar percentages, 10～35% molar percentages respectively at this liquid crystal polyester:
(1)-O-Ar
1-CO-
(2)-CO-Ar
2-CO-
(3)-X-Ar
3-Y
Ar wherein
1Expression 1,4-phenylbenzene, 2,6-base or 4,4 '-two phenylbenzene, Ar
2Expression 1,4-phenylbenzene, 1,3-phenylbenzene or 2,6-naphthyl, Ar
3Expression 1,4-phenylbenzene or 1,3-phenylbenzene, X represent-NH-, and Y represents-O-or-NH-.
3, liquid crystal polyester liquid constituent according to claim 1 and 2, the amount that it is characterized in that wherein said liquid crystal polyester are between 0.01 to 100 part of weight, and it is for this non-protonic solvent of 100 parts of weight.
4, liquid crystal polyester liquid constituent according to claim 1 and 2 is characterized in that wherein said non-protonic solvent is for not having the non-protonic solvent of halogen atom.
5, liquid crystal polyester liquid constituent according to claim 1 and 2 is characterized in that wherein said non-protonic solvent is is 3～5 non-protonic solvent for having moment of dipole.
6, liquid crystal polyester liquid constituent according to claim 5 is characterized in that wherein said to have moment of dipole be that 3～5 non-protonic solvent is to be ester solvent in an acid amide solvent or.
7, liquid crystal polyester liquid constituent according to claim 6 is characterized in that wherein said acid amide solvent is to be selected from N, N '-dimethyl formamide, N, N '-N,N-DIMETHYLACETAMIDE and N-methyl cough up cohort that pyridine ketone formed one of them.
8, liquid crystal polyester liquid constituent according to claim 2 is characterized in that wherein said Ar
1Be to be 2,6-naphthyl, Ar
2Be to be 1,3-phenylbenzene, Ar
3Be to be 1,4-phenylbenzene, X are to be-NH-, and Y is-O-.
9, a kind of method of producing liquid crystal polyester thin film is characterized in that it may further comprise the steps: described this solution composition thing of claim 1 is coated on the upholder; And remove this solvent.
10, a kind of liquid crystal polyester thin film is characterized in that it is the method production by the described production liquid crystal polyester thin film of claim 9.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003112510 | 2003-04-17 | ||
| JP2003112510A JP4470390B2 (en) | 2003-04-17 | 2003-04-17 | Liquid crystalline polyester solution composition |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2007101300588A Division CN101104705B (en) | 2003-04-17 | 2004-04-13 | Liquid crystal polyester thin film and producing method thereof |
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| CN1537919A true CN1537919A (en) | 2004-10-20 |
| CN100370006C CN100370006C (en) | 2008-02-20 |
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| CN2007101300588A Expired - Lifetime CN101104705B (en) | 2003-04-17 | 2004-04-13 | Liquid crystal polyester thin film and producing method thereof |
| CNB2004100316960A Expired - Fee Related CN100370006C (en) | 2003-04-17 | 2004-04-13 | Liquid crystal polyester solution composition |
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| Application Number | Title | Priority Date | Filing Date |
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| CN2007101300588A Expired - Lifetime CN101104705B (en) | 2003-04-17 | 2004-04-13 | Liquid crystal polyester thin film and producing method thereof |
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| Country | Link |
|---|---|
| US (1) | US7022807B2 (en) |
| JP (1) | JP4470390B2 (en) |
| KR (1) | KR101114811B1 (en) |
| CN (2) | CN101104705B (en) |
| DE (1) | DE102004018333A1 (en) |
| TW (1) | TWI356834B (en) |
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-
2003
- 2003-04-17 JP JP2003112510A patent/JP4470390B2/en not_active Expired - Lifetime
-
2004
- 2004-04-06 TW TW093109444A patent/TWI356834B/en not_active IP Right Cessation
- 2004-04-13 CN CN2007101300588A patent/CN101104705B/en not_active Expired - Lifetime
- 2004-04-13 CN CNB2004100316960A patent/CN100370006C/en not_active Expired - Fee Related
- 2004-04-14 KR KR1020040025907A patent/KR101114811B1/en active IP Right Grant
- 2004-04-15 US US10/824,475 patent/US7022807B2/en not_active Expired - Lifetime
- 2004-04-15 DE DE102004018333A patent/DE102004018333A1/en not_active Ceased
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1903564B (en) * | 2005-07-29 | 2010-11-10 | 住友化学株式会社 | Laminate of liquid crystalline polyester and copper foil |
| CN109504116A (en) * | 2017-09-14 | 2019-03-22 | 佳胜科技股份有限公司 | liquid crystal polymer composition and high-frequency composite substrate |
Also Published As
| Publication number | Publication date |
|---|---|
| US20040210032A1 (en) | 2004-10-21 |
| DE102004018333A1 (en) | 2004-11-04 |
| JP4470390B2 (en) | 2010-06-02 |
| US7022807B2 (en) | 2006-04-04 |
| TWI356834B (en) | 2012-01-21 |
| TW200422346A (en) | 2004-11-01 |
| KR20040090717A (en) | 2004-10-26 |
| CN100370006C (en) | 2008-02-20 |
| CN101104705A (en) | 2008-01-16 |
| CN101104705B (en) | 2010-10-27 |
| KR101114811B1 (en) | 2012-02-15 |
| JP2004315678A (en) | 2004-11-11 |
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